Apparatus for reforming hydrocarbon fuels to produce hydrogen

ABSTRACT

Apparatus for reforming hydrocarbon fuels by admixing a hydrocarbon and water to form a feedstream, contacting the feedstream with an inorganic salt or mixture of inorganic salts in the molten state, and separating the gaseous effluent generated by this contact. After the hydrogen-containing effluent is removed from the molten salt, means are provided that the latter may be mixed with oxygen at a temperature and pressure sufficient to permit combustion between the oxygen and any residual carbon which may be retained in the salt, after which further means are provided to remove the gaseous reaction products of this combustion.

United States Patent Inventors Mohendra S. Bawa;

James K. Trultt, both of Dallas, Tex. Appl. No.

Filed Sept. 15, 1969 Division of Ser. No. 590,813, Oct. 31, 1966, Pat. No. 3,505,018

Patented Nov. 9, 1971 Assignee Texas Instruments Incorporated Dallas, Tex.

APPARATUS FOR REFORMING HYDROCARBON FUELS T0 PRODUCE HYDROGEN 5 Claims, 2 Drawing Figs.

US. Cl 23/282, 23/212, 23/288, 48/61, 48/214,136/86, 252/373 Int. Cl C0lb 1/16, HOlm 27/20 Field of Search 23/21 1,

212, 212 A, 212 B, 288, 282, 284;48/2l4, 61; 252/373; 136/86 FRESH SALT FEED TEST SAMPLE AIR "I 56] Relerences Cited UNITED STATES PATENTS 3,106,457 10/1963 Lockerbie et a1 23/212 3,147,080 9/1964 Jahnig 23/212 3,313,598 4/1967 Gluckstein 23/211 3,453,146 7/1969 Bawa et al. 48/214X 1 Primary Examiner-Morris O. Wolk Assistant Examiner-R. E. Serwin Anvrneys1ames 0. Dixon, Andrew M. Hassell, Harold Levine, Rene E. Grossman, Richards, Harris and Hubbard and V. Bryan Medlock, Jr.

ABSTRACT: Apparatus for reforming hydrocarbon fuels by admixing a hydrocarbon and water to form a feedstream, contacting the feedstream with an inorganic salt or mixture of inorganic salts in the molten state, and separating the gaseous effluent generated by this contact. After the hydrogen-contaming effluent is removed from the molten salt, means are provided that the latter may be mixed with oxygen at a temperature and pressure sufficient to permit combustion bdtween the oxygen and any residual carbon which may be 1 retained in the salt, after which further means are provided to remove the gaseous reaction products of this combustion.

TO CATHODES 3.TO ANODES MIN -+11 0 SPENT SALT ms'cmmcs PATENTEUNUV 9 IBTI as FRESH SALT 34 3 TO CATHODES FEED /8 ,2! -'-'\-T0 ANODES TEST SAMPLE .CHZ.+HZO

AIR

SPENT SALT 7-: DISCHARGE 2 a B z /"O O o I 37 f 5 T0 T0 CATHODES MODES OR WASTE FIG. 2

INVENTOR MOHENDRA S. BAWA JAMES K. TRUITT APPARATUS FOR REFORMING HYDROCARBON FUELS T PRODUCE HYDROGEN This is a division of copending application Ser. No. 590,8 l 3 filed Oct. 31, 1966, and now U.S. Pat. No. 3,505,0l8.

This invention relates to a method and apparatus for producing hydrogen, and more particularly, but not by way of limitation to a method and apparatus for reforming hydrocarbon fuels to produce hydrogen for fuel cells and the like.

Direct conversion of hydrocarbon fuels to electrical energy by various types of fuel cells and fuel cell systems has been proposed by the prior art. While most fuel cells use only pure hydrogen for fuel, there have been developed recently fuel cells capable of using an impure hydrogen stream, such as one having carbon monoxide in addition to hydrogen. However, conversion of hydrocarbon fuels to a suitable impure hydrogen fuel has heretofore involved expensive, bulky and complex equipment. For example, conversion of gaseous hydrocarbons to impure hydrogen may be accomplished by partial oxidation of hydrocarbons. However, careful control of the reaction is required to prevent carbon formation and the reaction must be carried out at temperatures in excess of l200 C.

Another classic conversion process known as steam reforming of hydrocarbons" has also been used. In this process steam is reacted with a hydrocarbon fuel to produce molecular hydrogen and carbon monoxide. This reaction, however, is endothermic and has therefore been practiced in the past with the use of a catalyst at temperatures between about 350 C. and 750 C. The catalyst used in such steam reforming reactions have been catalysts such as nickel and nickel alloys which are easily poisoned by impurities such as elemental or combined sulfur which is commonly found in most commercial hydrocarbon fuels.

While the steam reforming of all hydrocarbon fuels is thermodynamically feasible, with high molecular weight alkyl hydrocarbons and olefins, carbon will be deposited in the steam reforming process. The carbon thus produced can build up and render the equipment ineffective.

The present invention provides a method and apparatus to produce hydrogen from a wide variety of hydrocarbon fuels, including high molecular weight alkyl hydrocarbons and olefins without the buildup of elemental carbon. The process and apparatus is particularly useful in producing hydrogen from sulfur containing hydrocarbons without the usual problems of sulfur contamination of catalysts.

The inventive method may generally be described as a method for producing hydrogen for fuel cells from hydrocarbons, comprising the steps of admixing a hydrocarbon fuel and water to form a feed stream. The feed stream is intimately contacted with an inorganic salt between 350 C. and 850 C.,

- and the gaseous effluent generated by the hydrocarbon fuel and water in contact with the liquid inorganic salt is removed from the salt. The molten salt is then, after removal of the effluent therefrom, mixed with oxygen at a temperature and pressure sufficient to permit combustion between the oxygen and any carbon retained in the salt, and the gaseous reaction products of the oxygen and carbon are removed.

Apparatus in accordance with the present invention may be generally described as including a first chamber which is partially filled with liquid or inorganic salt between 350 C. and 850 C. Means are provided for intimately admixing a feed stream ofat least one hydrocarbon fuel and water withthe liquid-salt for producing hydrogen. Means are also provided for removing from the first chamber the hydrogen produced therein and for circulating the salt in the first chamber to a second chamber and for returning the salt from the second chamber back to the first chamber. The salt contained in the second chamber is intimately mixed with oxygen for combusting any carbon retained in the salt, and the combustion product of the carbon and oxygen is removed from the second chamber. a

A particular advantage of the inventive method and apparatus is the high efficiency obtained at low temperatures while avoiding poisoning of any catalyst which may be used.

Other objects, features and advantages will become apparent after a reading of the following description taken in connection with the drawings, in which:

HO. 1 is a pictorial view in vertical section of apparatus embodying the present invention; and

FIG. 2 is also a pictorial view in vertical section of yet another apparatus embodying the present invention.

ln FIG. 1 a vertical container 3, which may be cylindrical in transverse cross section is provided with a plurality of trays 4- 6 all of which support a liquid inorganic salt 7 as does bottom 8 of the vessel. Salt 7 on tray 4 communicates with the salt 7 on tray 5 through a downspout 9, end ll of which protrudes above tray 4. Downspout 9 will serve to maintain a constant liquid level above tray 4. Tray 5, in turn, communicates with tray 6 through a downspout 12, end 13 of which protrudes above tray 5 to determine the liquid level above tray 5. Tray 6, in turn, communicates with the bottom of vessel 3 through a downspout l4, and 10 of which extends above tray 6 to determine the liquid level ofsalt 7 above tray 6. A hydrocarbon fuel and water, preferably in the form of steam, are fed through conduit 15 into the salt 7 on tray 6 through a conventional bubble cap 16 which disperses the material in salt 7 permitting intimate contact therebetween. In the presence of the molten salt which is preferably maintained between 350 C. and 850 C., the hydrocarbon fuel which may generally be identified by the formula CH and water will undergo the following reactions:

l. -CH H 0-'CO+2H 2. -CH C+H The gaseous effluent of CO, H and any unreacted hydrocarbon fuel and water from tray 6 will flow through vapor space 17 above tray 6 within which is supported a mesh (Tyler series) nickel screen 6' which supports a plurality of foraminous nickel strips 6" such as may be formed by cutting squares from a mesh (Tyler series) nickel screen. The nickel serves to catalyze the reformation, and the gaseous effluent after passing through screen 6' and strips 6" will pass through conventional bubble cap 18 on tray 5. Bubble cap 18 disperses the gaseous effluent in the bed of salt 7 on tray 5 to intimately contact the gases and salt to permit further reformation of the hydrocarbon fuel. The gaseous effluent from salt 7 on tray 5 will exit the vapor space 19 above tray 5, within which are supported a nickel screen 5 and nickel strips 5", through conduit 21 which may be communicated with the anode of a conventional hydrogen fuel cell such as those described in Electrode Processes in Molten Carbonate Fuel cells," Advances in Chemistry Series, No. 47, page 232, published by the American Chemical Society, Washington, D.C.( 1965). The nickel screen 5' and strips 5" serve to further catalyze the reforming of the feed stream. Salt 7 which may be molten inorganic salt such as carbonates of sodium, potassium, or lithium or mixtures thereof or mixtures of such carbonate salts with sulfate salts of sodium, potassium or lithum serve as a heat transfer agent to improve efficiency of the steam reforming of hydrocarbon fuel and also serves as an aid in cracking any aromatic and branched chain hydrocarbons in the feed stream to make them more suitable for the reforming reaction. Furthermore, the molten salt further serves to remove sulfur and lead compounds from the hydrocarbon fuel to prevent contamination of the gas exiting to the anode of a fuel cell. The sulfur impurities which may be generally represented by the formula 'S is believed to undergo the following reactions in the presence of a carbonate salt:

3. -S-+CO SO +CO The sulfite thus produced will undergo further reaction, as will be explained later. The reaction by which other inorganic salts entrain the sulfur contaminants is not understood, but they are effective nonetheless. Salt 7 on tray 5 and tray 6, which will contain any carbon formed during the reforming of the hydrocarbon fuel, as well as any sulfur contaminant in the fuel will, as explained before, flow through downspouts l2 and 14 into bottom 20 of container 3. Bottom 20 of container 3 is provided with a foraminous truncated spherical-shaped shell 22 having an integral conduit 23 which rises through trays 46. Conduit 23 is sealingly affixed to trays 4-6 at points 2426, respectively. The carbon and sulfur laden salt 7 contained in the bottom 20 of container 3 will enter shell 22 through the apertures 27 and be lifted through conduit 23 by air introduced into container 3 through conduit 28. Air in conduit 28 discharges through nozzle 29 proximate the bottom end of conduit 23 to serve as a lifting agent for salt 7. To assure that pressure in the vapor space of bottom 20 does not force salt through conduit 23, there is provided a pressure equalization conduit 8 which communicates bottom 20 and vapor space 32 above tray 4. Nozzle 29 disperses the air within the salt to intimately mix the salt and air. The air, which serves as an economical source of oxygen, reacts with the entrained carbon by the following reaction:

4. C+ -l-4N,...2CO +4N The sulfite retained by the salt 7 is believed to undergo the following reaction in the presence of the air:

5.- QT +Q2 iii iz The gaseous byproducts of the combustion between the entrained carbon and oxygen in the air stream will exit the top 31 of conduit 23 into vapor space 32 above tray 4 from which it flows through conduit 33 to the cathode of a conventional fuel cell, such as those described in the article Electrode Processes in Molten Carbonate Fuel Cells," cited above, or to v preceded in reactions 3 and above. The combustion product a waste stream. Salt 7 exiting top 31 of conduit 23 will flow through downspout 11 onto tray 6 to provide a carbon-free salt on the reformer trays 5 and 6.

Since the sulfur contained in salt 7 will gradually build up as entrained sulfates, the container 3 preferably has fresh salt feed conduit 34 through which fresh salt may be fed and a spent salt discharge conduit 35 through which salt may be removed to prevent build up within container 3. The amount of salt to be fed to container 3 to prevent build up of sulfates in the salt 7 will depend upon the degree of sulfur content of the hydrocarbon fuel utilized. The salt may be replaced periodically or continuously. Vapor space 17 above tray 6 preferably communicates through a conduit 36 with means for periodically testing the degree of reforming of hydrocarbon fuel.

In FIG. 2, another embodiment of apparatus for carrying out the method of the present invention is illustrated. With reference to FIG. 2, a vertical cylindrical container 37, which like container 3 may be circular in transverse cross section, is provided with a substantially vertical partition 38 having a top opening 39 positioned proximate but below the surface of inorganic molten salt 7 which partially fills container 37. Partition 38 is also provided with an opening 39 proximate the bottom thereof and serves to divide the container 37 into a first chamber 42 and a second chamber 43. Partition 38 is provided with an oblique lip 44 proximate the top opening 39, the purpose of which will be described hereafter. A hydrocarbon fuel and stream feed stream is introduced through conduit 45 and dispersed by a sintered nickel foraminous nozzle 46 to permit intimate contact between the feed stream and the salt 7 in chamber 42. There may be provided, to assure complete reforming of the hydrocarbon stream a catalyst supported on a nickel screen secured across first chamber 42 by any suitable means (not illustrated). The catalyst supported by nickel screen 47 may take the form of a plurality of foraminous nickel strips such is may be formed by cutting a 125 mesh (Tyler series) screen into A inch square sections. The screen 47 and sections 48 may be formed of any conventional catalyst such as nickel alloys or chrome steel, as well as nickel. The gaseous effluent from the reformed hydrocarbon, namely CO and H will exit chamber 42 through conduit 49 which may direct it to the anodes of a fuel cell such as mentioned in Electrode Processes in Molten Carbonate Fuel Cells," cited above. Carbon deposited in the molten salt 7 during the reformation of the hydrocarbon fuel will be burned by air entering chamber 43 through conduit 51 and be dispersed through salt 7 by a foraminous nozzle 53 of stainless steel, and any sulfur containing compounds entrained in molten salt 7 will be converted to sulfates in the same manner as the conversion of the carbon and oxygen in the air will exit chamber 43 through conduit 52 to the cathodes of a fuel cell or may be exhausted to the atmosphere. The baffle 44, described above, aids in preventing the flow of gas from chamber 43 into chamber 42 to avoid contamination of the anode stream. The salt 7 in chamber 37 may be periodically replaced through feed and exhaust lines (not illustrated).

Various inorganic salts, such as those mentioned above may be utilized, it only being necessary that they be molten between 350 C. and 850 C. and provide a suitable heat transfer agent to assist in the reforming of hydrocarbon fuels. It is also preferable that the steam introduced to the hydrocarbon fuel feed be maintained between 350 C. and 850 C. and preferably take the form of a super-heated steam at atmospheric pressure. It is also preferable that approximately 1-2 moles of water be added to the hydrocarbon fuel stream for each carbon atom in the hydrocarbon fuel to maximum reforming of the hydrocarbon fuel.

The salt preferably used is sodium-lithium carbonate (Nat.- iCO Various hydrocarbon fuels may be employed with the present invention, including kerosene, .lP-4, CITE Fuel, leaded gasoline, diesel fuel, No. 2 fuel oil, ethane, propane, butane, and straight chain liquid alkyl hydrocarbons, as well as olefins. A catalyst may be used in either of the embodiments illustrated in FIGS. 1 or 2, since the sulfur contaminants which may be charged to ether of the units through the hydrocarbon fuel stream will be converted to sulfates which are not contaminants for the nickel, nickel alloys, or chrome steel conventional catalyst.

The exact reaction by which the salts mentioned above remove lead is not known, but it is believed that lead salts are formed which will be retained within the salt 7. While the invention has been described in connection with producing hydrogen for fuel cells, it may also be used in producing hydrogen for general purposes, including the synthesis of ammonia and methanol. Also, while the embodiment of FIG. 1 utilizes two reforming trays, more or less may be used depending upon the kinetics of the system.

While various terms have been used to describe illustrative embodiments of the apparatus, as well as embodiments of the method of the present invention, they are not intended, nor should they be construed, as limitation on the invention an defined by the claims.

We Claim:

1. Apparatus for producing hydrogen from hydrocarbons, comprising the combination of:

a first and second chamber;

a liquid inorganic salt between 350 C. and 850 C. partially filling said chamber,

means for intimately admixing a feed stream of at least one hydrocarbon fuel and water with said liquid salt for producing hydrogen;

means for removing from said first chamber the hydrogen produced therein;

means for circulating the salt in said first chamber to said second chamber and from said second chamber back to said first chamber;

means for intimately mixing said salt in said second chamber with oxygen for combusting carbon in said salt; and

means for removing the combustion product of carbon and oxygen from said second chamber.

2. The apparatus of claim 1, wherein said means for circulating salt between said first and second chambers, comprises:

a generally vertically oriented conduit one end of which terminates below the liquid level of the salt in said second chamber and the other end of which communicates with said first chamber; and

a nozzle which discharges said oxygen within said conduit proximate the bottom end of said conduit for lifting liquid salt through said conduit and out the upper end thereof.

fuel and water proximate the bottom of said first chamber for producing hydrogen;

means for removing hydrogen from said first chamber;

means for introducing oxygen into said second chamber proximate the bottom thereof for permitting combustion between the oxygen and the carbon in said liquid salt; and

means for removing said combustion product from said second chamber.

5. The device of claim 4, wherein:

said partition is provided with an oblique lip proximate the top opening therein to minimize commingling of gases produced in said first and second chambers. 

2. The apparatus of claim 1, wherein said means for circulating salt between said first and second chambers, comprises: a generally vertically oriented conduit one end of which terminates below the liquid level of the salt in said second chamber and the other end of which communicates with said first chamber; and a nozzle which discharges said oxygen within said conduit proximate the bottom end of said conduit for lifting liquid salt through said conduit and out the upper end thereof.
 3. The device of claim 2, including means for equalizing pressure between said first and second chambers.
 4. Apparatus for producing hydrogen from hydrocarbons, comprising the combination of: a container; a liquid inorganic salt between 350* and 850* C. partially filling said container; substantially vertical partition means dividing said container into first and second chambers, said partition means being provided with a top opening therein beneath but proximate the surface of said salt and a bottom opening for permitting circulation of salt between said first and second chambers; means for introducing a mixture of at least one hydrocarbon fuel and water proximate the bottom of said first chamber for producing hydrogen; means for removing hydrogen from said first chamber; means for introducing oxygen into said second chamber proximate the bottom thereof for permitting combustion between the oxygen and the carbon in said liquid salt; and means for removing said combustion product from said second chamber.
 5. The device of claim 4, wherein: said partition is provided with an oblique lip proximate the top opening therein to minimize commingling of gases produced in said first and second chambers. 